Hydrocarbon Conversion Process Using a High Throughpout Process for Manufacturing Molecular Sieves

ABSTRACT

A method of crystallizing a crystalline molecular sieve having a pore size in the range of from about 2 to about 19 Å, said method comprising the steps of (a) providing a mixture comprising at least one source of ions of tetravalent element (Y), at least one hydroxide source (OH − ), and water, said mixture having a solid-content in the range of from about 15 wt. % to about 50 wt. %; and (b) treating said mixture to form the desired crystalline molecular sieve with stirring at crystallization conditions sufficient to obtain a weight hourly throughput from about 0.005 to about 1 hr −1 , wherein said crystallization conditions comprise a temperature in the range of from about 200° C. to about 500° C. and a crystallization time less than 100 hr.

CROSS REFERENCE TO RELATED APPLICATION

This application claims priority to U.S. Provisional Patent ApplicationNo. 60/773,198, filed Feb. 14, 2006, the disclosures of which areincorporated herein by reference in its entirety.

FIELD

This invention relates to a high throughput process of manufacturingmolecular sieves and the use of the same for hydrocarbon conversions.

BACKGROUND OF THIS INVENTION

Molecular sieve materials, both natural and synthetic, have beendemonstrated in the past to have catalytic properties for various typesof hydrocarbon conversion. Certain molecular sieves (e.g. zeolites,AIPOs, or mesoporous materials) are ordered, porous crystallinealuminosilicates having a definite crystalline structure as determinedby X-ray diffraction. Since the dimensions of these pores are such as toaccept for adsorption molecules of certain dimensions while rejectingthose of larger dimensions, these materials have come to be known as“molecular sieves” and are utilized in a variety of industrialprocesses. The pores in microporous crystalline molecular sievesnormally have a cross section dimension from about 2 Å to about 19 Å.This as opposed to mesoporous molecular sieves which have pore sizesbetween 20 Å and 1000 Å.

Molecular sieves that find application in catalysis include any of thenaturally occurring or synthetic crystalline molecular sieves. Examplesof these zeolites include large pore zeolites, intermediate pore sizezeolites, and small pore zeolites. These zeolites and their isotypes aredescribed in “Atlas of Zeolite Framework Types”, eds. W. H. Meier. D. H.Olson and Ch. Baerlocher, Elsevier, Fifth Edition. 2001, which is herebyincorporated by reference. A large pore zeolite generally has a poresize of at least about 7 Å and includes LTL, VFI, MAZ, FAU, OFF, *BEA,and MOR framework type zeolites (IUPAC Commission of ZeoliteNomenclature). Examples of large pore zeolites include mazzite,offretite, zeolite L, VPI-5, zeolite Y, zeolite X, omega, and Beta. Anintermediate pore size zeolite generally has a pore size from about 5 Åto less than about 7 Å and includes, for example, MFI, MEL, EUO, MTT,MFS, AEL, AFO, HEU, FER, MWW, and TON framework type zeolites (IUPACCommission of Zeolite Nomenclature). Examples of intermediate pore sizezeolites include ZSM-5, ZSM-11, ZSM-22, MCM-22, silicalite 1, andsilicalite 2. A small pore size zeolite has a pore size from about 3 Åto less than about 5.0 Å and includes, for example, CHA, ERI, KFI, LEV,SOD, and LTA framework type zeolites (IUPAC Commission of ZeoliteNomenclature). Examples of small pore zeolites include ZK-4, ZSM-2,SAPO-34, SAPO-35, ZK-14, SAPO-42, ZK-21, ZK-22, ZK-5, ZK-20, zeolite A,chabazite, zeolite T, gmelinite, ALPO-17, and clinoptilolite.

Synthetic molecular sieves are often prepared from aqueous reactionmixtures (synthesis mixtures) comprising sources of appropriate oxides.Organic directing agents (“structure directing agent”) may also beincluded in the synthesis mixture for the purpose of influencing theproduction of a molecular sieve having the desired structure. The use ofsuch directing agents is discussed in an article by Lok et al. entitled“The Role of Organic Molecules in Molecular Sieve Synthesis” appearingin Zeolites, Vol. 3, October, 1983, pp. 282-291.

After the components of the synthesis mixture are properly mixed withone another, the synthesis mixture is subjected to appropriatecrystallization conditions in an autoclave. Such conditions usuallyinvolve heating of the synthesis mixture to an elevated temperaturepossibly with stirring. Room temperature aging of the synthesis mixtureis also desirable in some instances.

After the crystallization of the synthesis mixture is complete, thecrystalline product may be recovered from the remainder of the synthesismixture, especially the liquid contents thereof. Such recovery mayinvolve filtering the crystals and washing these crystals with water.However, in order to remove the entire undesired residue of thesynthesis mixture from the crystals, it is often necessary to subjectthe crystals to a high temperature calcination e.g., at 540° C.,possibly in the presence of oxygen. Such a calcination treatment notonly removes water from the crystals, but this treatment also serves todecompose and/or oxidize the residue of the organic directing agentwhich may be occluded in the pores of the crystals, possibly occupyingion exchange sites therein.

However, synthetic molecular sieves are expensive. A need exists for ahigh throughput process of manufacturing molecular sieves. Thisinvention discloses a high throughput process of manufacturing molecularsieves by the combination of high solid content and high temperature.Such method of manufacturing has the advantage of low cost, shortcrystallization time, and high yield.

SUMMARY OF THIS INVENTION

In one embodiment, this invention relates to a method of crystallizing acrystalline molecular sieve having a pore size in the range of fromabout 2 to about 19 Å, said method comprising the steps of:

-   (a) providing a mixture comprising at least one source of ions of    tetravalent element (Y), at least one hydroxide source (OH⁻), and    water, said mixture having a solid-content in the range of from    about 15 wt. % to about 50 wt. %; and-   (b) treating said mixture to form the desired crystalline molecular    sieve with stirring at crystallization conditions sufficient to    obtain a weight hourly throughput from about 0.005 to about 1 hr⁻¹,    wherein said crystallization conditions comprise a temperature in    the range of from about 200° C. to about 500° C. and a    crystallization time less than 100 hr.

In another embodiment, this invention relates to a process ofmanufacturing a crystalline molecular sieve having a pore size in therange of from about 2 to about 19 Å, said method comprising the stepsof:

-   (a) providing a mixture comprising at least one source of ions of    tetravalent element (Y), at least one hydroxide source (OH⁻), and    water, said mixture having a solid-content in the range of from    about 15 wt. % to about 50 wt. %;-   (b) treating said mixture to form the desired crystalline molecular    sieve with stirring at crystallization conditions sufficient to    obtain a weight hourly throughput from about 0.005 to about 1 hr⁻¹,    wherein said crystallization conditions comprise a temperature in    the range of from about 200° C. to about 500° C. and a    crystallization time less than 100 hr; and-   (c) separating said crystalline molecular sieve from said product.

In yet another embodiment, this invention relates to a crystallinemolecular sieve composition having a pore size in the range of fromabout 2 to about 19 Å, said crystalline molecular sieve composition madeby a process comprising the steps of:

-   (a) providing a mixture comprising at least one source of ions of    tetravalent element (Y), at least one hydroxide source (OH⁻), and    water, said mixture having a solid-content in the range of from    about 15 wt. % to about 50 wt. %;    -   (b) treating said mixture to form the desired crystalline        molecular sieve with stirring at crystallization conditions        sufficient to obtain a weight hourly throughput from about 0.005        to about 1 hr⁻¹, wherein said crystallization conditions        comprise a temperature in the range of from about 200° C. to        about 500° C. and a crystallization time less than 100 hr, and    -   wherein said crystalline molecular sieve is substantially free        of non-crystalline material.

In an embodiment, this invention relates to a process for convertinghydrocarbons comprising the step of contacting said hydrocarbons withsaid crystalline molecular sieve manufactured by the process describedabove under conversion conditions.

These and other facets of the present invention shall become apparentfrom the following detailed description, figure, and appended claims.

DESCRIPTION OF THE FIGURE

FIG. 1 is X-ray diffraction pattern of the crystalline material productof example 2.

FIG. 2 is SEM image of the crystalline material product of example 2.

DETAILED DESCRIPTION OF THIS INVENTION Crystalline Molecular Sieve

The term “throughput” used herein means the amount of crystallinemolecular sieve produced per unit time (hour) and per unit volume of thesynthesis mixture (volume hourly throughput) or per unit weight of thesynthesis mixture (weight hourly throughput). The higher the throughput,the more crystalline molecular sieve produced per unit volume of thereactor and per unit amount of time. Therefore, for the same amount ofthe crystalline molecular sieve synthesized, the higher the throughput,generally the smaller the reactor (autoclave) needed or the shorter thetime required for each synthesis. The volume hourly throughput for asynthesis may be calculated by dividing the weight of the molecularsieve produced in the dried cake (the solid product aftercrystallization dried at 120° C. for 24 hours) with the volume of thesynthesis mixture and the total time required for the crystallization(hereinafter “cycle time required for the crystallization”). The cycletime required for the crystallization is the time required forcrystallization under the crystallization conditions, which does notinclude the time for aging the synthesis mixture, filtering, washing,and drying the product. The volume hourly throughput for a synthesis iscalculated as following:

${{volume}\mspace{14mu} {hourly}\mspace{14mu} {throughput}} = \frac{\begin{matrix}{{weight}\mspace{14mu} {of}\mspace{11mu} {the}\mspace{14mu} {molecular}} \\{{sieve}\mspace{14mu} {in}\mspace{14mu} {the}\mspace{14mu} {dried}\mspace{14mu} {cake}}\end{matrix}}{\begin{matrix}{\left( {{volume}\mspace{14mu} {of}\mspace{14mu} {the}\mspace{14mu} {synthesis}\mspace{14mu} {mixture}} \right) \times} \\\left( {{cycle}\mspace{14mu} {time}} \right)\end{matrix}}$

The weight hourly throughput for a synthesis may be calculated byexpressing the amount of tetravalent element in terms of its oxide anddividing the weight of the oxide of tetravalent element (YO₂), e.g.,SiO₂, used in the dried cake (the solid product after crystallizationdried at 120° C. for 24 hours) with the weight of the water used in thecrystallization and the cycle time required for the crystallization asfollowing:

$\begin{matrix}{{weight}\mspace{14mu} {hourly}} \\{throughput}\end{matrix} = \frac{{weight}\mspace{14mu} {of}\mspace{14mu} {the}\mspace{14mu} {YO}_{2} \times {silica}\mspace{14mu} {utilization}}{\left( {{weight}\mspace{14mu} {of}\mspace{14mu} {the}\mspace{14mu} {water}} \right) \times \left( {{crystallization}\mspace{14mu} {time}} \right)}$

Typical silica utilization for crystallizations is about 85%.

In one embodiment, this invention has a weight hourly throughput of atleast about 0.005 hr⁻¹, preferably at least about 0.008 hr⁻¹, morepreferably at least about 0.01 hr⁻¹, even more preferably at least about0.02 hr⁻¹, and most preferably at least about 0.05 hr⁻¹. Optionally,this invention has a weight hourly throughput less than 1 hr⁻¹ or lessthan 0.5 hr⁻¹.

The weight hourly throughput of a synthesis may be adjusted by changingsolid-content, amount of seed used in the synthesis gel, crystallizationtemperature, time for crystallization, and/or any combination thereof.The weight hourly throughput and these parameters mentioned above areinterrelated. Changing one parameter may affect other parameters. Forexample, by increasing weight hourly throughput of a synthesis undercertain crystallization conditions, e.g., crystallization temperatureand time, the solid-content and/or the amount of seed crystal may haveto increase.

One factor affecting the synthesis of a crystalline molecular sieve isthe solid-content in a synthesis mixture. The term “solid-content” usedherein means the weight ratio of the tetravalent element and thetrivalent element when present in the synthesis mixture, expressed interms of their oxides, over the water in the synthesis mixture inpercentage. It can be measured by dividing the weight of the oxides inthe synthesis mixture by the weight of the water in the synthesismixture as following:

${{solid}\text{-}{content}} = \frac{\begin{matrix}{{the}\mspace{14mu} {weight}\mspace{14mu} {of}\mspace{14mu} {the}\mspace{14mu} {oxides}} \\{{in}\mspace{14mu} {the}\mspace{14mu} {synthesis}\mspace{14mu} {mixture}}\end{matrix}}{{weight}\mspace{14mu} {of}\mspace{14mu} {the}\mspace{14mu} H_{2}O\mspace{14mu} {in}\mspace{14mu} {the}\mspace{14mu} {synthesis}\mspace{14mu} {mixture}}$

The term “high solid” used herein means that the solid-content of asynthesis mixture is at least 15 wt. %, preferably at least 18 wt. %,more preferably at least 20 wt. %, even more preferably at least 25 wt.%, and most preferably at least 30 wt. %. The solid content useful inthis invention includes a range from at least about 15 wt. %, preferablyat least about 18 wt. %, more preferably at least about 20 wt. %, evenmore preferably at least about 25 wt. %, and most preferably at leastabout 30 wt. % to less than 50 wt. %, preferably less than about 45 wt.%, more preferably less than about 40 wt. %, and most preferably lessthan about 35 wt. %.

It will be understood by a person skilled in the art that the synthesismixture having a composition within the ranges as discussed above meansthat the synthesis mixture is the product of mixing, adding, reacting,or by any means of providing a mixture, wherein such product has acomposition within the ranges as discussed above. The product of mixing,adding, reacting, or by any means of providing a mixture may or may notcontaining individual ingredients when the product was prepared. Theproduct of mixing, adding, reacting, or by any means of providing amixture, may even containing reaction product of individual ingredientswhen the product was prepared by mixing, adding, reacting, or by anymeans of providing a mixture.

Another factor affecting the synthesis of a crystalline molecular sieveis the temperature. High temperature, e.g., greater than 200° C., maydamage the directing agent in the synthesis mixture. To performcrystallization at high temperature, more directing agent may be neededsince some of the directing agent might be damaged by the causticreactant(s) in the synthesis mixture at the high temperature. Generally,the higher the temperature, the faster the crystallization rate.However, higher temperature may damage the expensive directing agent,which may impact the product quality, e.g. final product containingimpurities. The term “high temperature” as used herein means thecrystallization temperature ranges from at least about 180° C.,preferably at least about 190° C., more preferably at least about 200°C., even more preferably at least about 225° C., and most preferably atleast about 230° C. to less than 500° C. preferably less than 400° C.,more preferably less than 300° C., and most preferably less than 250° C.Another disadvantage of high temperature is narrow crystallizationwindow.

The mixture used for synthesis of the molecular sieve may comprise astructure directing agent (template). A factor affecting the cost andthe product quality of the synthesis of a crystalline molecular sieve isthe amount of the directing agent. The directing agent is generally themost expensive reactant(s) in the synthesis mixture of many crystallinemolecular sieves. The lower the amount of the directing agent in thesynthesis mixture, the cheaper the final molecular sieve produced. Theterm “low directing agent” as used herein means the molar ratio of thedirecting agent over the tetravalent element in the synthesis mixture isless than 0.5, preferably less than 0.34, even more preferably less than0.2, and most preferably less than 0.15.

The term “weight hourly template efficiency” used herein means theweight of crystalline molecular sieve produced per weight of directingagent used per unit time (hour). The higher the weight hourly templateefficiency, the more crystalline molecular sieve produced per unitweight of the directing agent used and per unit amount of time.Therefore, for the same amount of the crystalline molecular sievesynthesized, the higher the weight hourly template efficiency, generallythe cheaper the synthesis or the shorter the time required for eachsynthesis. The weight hourly template efficiency for a synthesis may becalculated by dividing the weight of the molecular sieve produced in thedried cake (the solid product after crystallization dried at 120° C. for24 hours) with the weight of the directing agent used in the synthesismixture and the total time required for the crystallization (“cycle timerequired for the crystallization”). The weight hourly templateefficiency for a synthesis is calculated as following:

$\begin{matrix}{{weight}\mspace{14mu} {hourly}} \\{{template}\mspace{14mu} {efficiency}}\end{matrix} = \frac{\begin{matrix}{{weight}\mspace{14mu} {of}\mspace{14mu} {the}\mspace{14mu} {oxide}\mspace{14mu} {of}} \\{{tetravalent}\mspace{14mu} {element}\mspace{14mu} \left( {YO}_{2} \right) \times} \\{{tetravalent}\mspace{14mu} {element}\mspace{14mu} {oxide}\mspace{14mu} {utilization}}\end{matrix}}{\begin{matrix}{\left( {{weight}\mspace{14mu} {of}\mspace{14mu} {the}\mspace{14mu} {directing}\mspace{14mu} {agent}} \right) \times} \\\left( {{crystallization}\mspace{14mu} {time}} \right)\end{matrix}}$

Typical tetravalent element oxide, e.g., silica, utilization forcrystallizations is about 85%.

In one embodiment, this invention has a weight hourly templateefficiency of at least about 0.035 hr⁻¹, preferably at least about 0.04hr⁻¹, more preferably at least about 0.05 hr⁻¹, even more preferably atleast about 0.08 hr⁻¹, and most preferably at least about 0.1 hr⁻¹.

The weight hourly template efficiency of a synthesis may be adjusted bychanging solid-content, amount of seed used in the synthesis gel, amountof template used in the synthesis gel, crystallization temperature, timefor crystallization, and/or any combination thereof. The weight hourlytemplate efficiency and these parameters mentioned above areinterrelated. Changing one parameter may affect other parameters. Forexample, by increasing weight hourly template efficiency of a synthesisunder certain crystallization conditions, e.g., crystallizationtemperature and time, the solid-content and/or the amount of seedcrystal may have to increase or the amount of seed used in the synthesisgel may have to decrease.

Optionally the synthesis mixture may contain seed crystals. It is wellknown that seeding a molecular sieve synthesis mixture frequently hasbeneficial effects, for example in controlling the particle size of theproduct, avoiding the need for an organic template, acceleratingsynthesis, and improving the proportion of product that is of theintended framework type. In one embodiment of this invention, synthesisof the crystalline molecular sieve is facilitated by the presence of atleast 0.01 wt. %, preferably 0.1 wt. %, more preferably 0.5 wt. %, evenmore preferably 1 wt. %, optionally from about 5 wt. % to about 20 wt.%, seed crystals based on total weight of silica of the synthesismixture.

We discovered an improved formulation for manufacturing crystallinemolecular sieves by the combination of high solid, high temperature, andoptionally low directing agent, seeding at improved crystallizationconditions including high temperature, stirring, and optionallyrecovering, recycling, and reusing the directing agent. By recovering,recycling, and reusing the directing agent, the synthesis mixture ofthis invention uses less costly, sometime toxic, directing agent.

In one embodiment, the crystalline molecular sieve manufactured by theprocess of this invention has a zeolite framework type comprising atleast one of ABW, AEI, AEL, AET, AFI, AFO, CHA, EMT, FAU, FER, LEV, LTA,LTL, MAZ, MEL, MTT, NES, OFF, TON, VFI, MWW, MTW, MFI, MOR, EUO, *BEA,and MFS. In another embodiment, the crystalline molecular sievemanufactured by the process of this invention has comprises at least oneof mordenite, MCM-22, MCM-49, MCM-56, ZSM-57, ZSM-5, ZSM-11, ZSM-12,ZSM-22, ZSM-23, ZSM-30, ZSM-48, ZSM-50, ZSM-48, ETS-10, ETAS-10, andETGS-10.

The term “MCM-22 family material” (or “material of the MCM-22 family” or“molecular sieve of the MCM-22 family”), as used herein, includes one ormore of:

-   (a) molecular sieves made from a common first degree crystalline    building block unit cell, which unit cell has the MWW framework    topology. (A unit cell is a spatial arrangement of atoms which if    tiled in three-dimensional space describes the crystal structure.    Such crystal structures are discussed in the “Atlas of Zeolite    Framework Types”, Fifth edition, 2001, the entire content of which    is incorporated as reference);-   (b) molecular sieves made from a common second degree building    block, being a 2-dimensional tiling of such MWW framework topology    unit cells, forming a monolayer of one unit cell thickness,    preferably one c-unit cell thickness;-   (c) molecular sieves made from common second degree building blocks,    being layers of one or more than one unit cell thickness, wherein    the layer of more than one unit cell thickness is made from    stacking, packing, or binding at least two monolayers of one unit    cell thickness. The stacking of such second degree building blocks    can be in a regular fashion, an irregular fashion, a random fashion,    or any combination thereof; and-   (d) molecular sieves made by any regular or random 2-dimensional or    3-dimensional combination of unit cells having the MWW framework    topology.

The MCM-22 family materials are characterized by having an X-raydiffraction pattern including d-spacing maxima at 12.4±0.25, 3.57±0.07and 3.42±0.07 Angstroms (either calcined or as-synthesized). The MCM-22family materials may also be characterized by having an X-raydiffraction pattern including d-spacing maxima at 12.4±0.25, 6.9±0.15,3.57±0.07 and 3.42±0.07 Angstroms (either calcined or as-synthesized).The X-ray diffraction data used to characterize said molecular sieve areobtained by standard techniques using the K-alpha doublet of copper asthe incident radiation and a diffractometer equipped with ascintillation counter and associated computer as the collection system.Materials belong to the MCM-22 family include MCM-22 (described in U.S.Pat. No. No. 4,954,325), PSH-3 (described in U.S. Pat. No. 4,439,409).SSZ-25 (described in U.S. Pat. No. 4,826,667), ERB-1 (described inEuropean Patent No. 0293032), ITQ-1 (described in U.S. Pat. No.6,077,498), ITQ-2 (described in International Patent Publication No.WO97/17290), ITQ-30 (described in International Patent Publication No.WO2005118476), MCM-36 (described in U.S. Pat. No. 5,250,277), MCM-49(described in U.S. Pat. No. 5,236,575) and MCM-56 (described in U.S.Pat. No. 5,362,697). The entire contents of said patents areincorporated herein by reference.

It is to be appreciated the MCM-22 family molecular sieves describedabove are distinguished from conventional large pore zeolite alkylationcatalysts, such as mordenite, in that the MCM-22 materials have 12-ringsurface pockets which do not communicate with the 10-ring internal poresystem of the molecular sieve.

The zeolitic materials designated by the IZA-SC as being of the MWWtopology are multi-layered materials which have two pore systems arisingfrom the presence of both 10 and 12 membered rings. The Atlas of ZeoliteFramework Types classes live differently named materials as having thissame topology: MCM-22, ERB-1, ITQ-1, PSH-3, and SSZ-25.

The MCM-22 family molecular sieves have been found to be useful in avariety of hydrocarbon conversion processes. Examples of MCM-22 familymolecular sieve are MCM-22, MCM-49, MCM-56, ITQ-1, PSH-3, SSZ-25, andERB-1. Such molecular sieves are useful for alkylation of aromaticcompounds. For example, U.S. Pat. No. 6,936,744 discloses a process forproducing a monoalkylated aromatic compound, particularly cumene,comprising the step of contacting a polyalkylated aromatic compound withan alkylatable aromatic compound under at least partial liquid phaseconditions and in the presence of a transalkylation catalyst to producethe monoalkylated aromatic compound, wherein the transalkylationcatalyst comprises a mixture of at least two different crystallinemolecular sieves, wherein each of said molecular sieves is selected fromzeolite beta, zeolite Y, mordenite and a material having an X-raydiffraction pattern including d-spacing maxima at 12.4±0.25, 6.9±0.15,3.57±0.07 and 3.42±0.07 Angstrom.

In another embodiment, the crystalline molecular sieve of this inventionhas a pore size in the range of from about 2 to about 19 Å, preferablyfrom about 2 to about 12 Å, and more preferably from about 4 to about 10Å.

It will be understood by a person skilled in the art that thecrystalline molecular sieve manufactured by the process of thisinvention may contain impurities, such as amorphous materials and/orother impurities (e.g., heavy metals and/or organic hydrocarbons). Thecrystalline molecular sieve manufactured by the process of thisinvention is preferably substantially free of non-crystalline material.The term “substantially free of non-crystalline material” used hereinmeans the crystalline molecular sieve preferably contains minorproportion (less than 50 wt. %), preferably less than 20 wt. %, morepreferably less than 10 wt. %, even more preferably less than 5 wt. %,and most preferably less than 1 wt. %, of such impuritiesnon-crystalline material based on the combined weight of impurities andcrystalline materials. The term “non-crystalline material” used hereinmeans any material does not contain crystalline molecular sieve.Examples of such non-crystalline material are amorphous microporousmaterial, amorphous mesoporous material, and amorphous macrostructurematerials.

In one embodiment, the crystallization conditions comprise a temperaturein the range of from about 200° C. to about 250° C., and crystallizationtime less than 72 hr, preferably less than 48 hours, more preferablyless than 24 hours, even more preferably less than 10 hours, and mostpreferably less than 5 hours.

In the present synthesis method, the source of ions of tetravalentelement (Y) preferably comprises solid oxide of the tetravalent element,YO₂, preferably about 30 wt. % solid YO₂ in order to obtain the crystalproduct of this invention. Examples of tetravalent element are silicon,germanium, and tin. When YO₂ is silica, the use of a silica sourcecontaining preferably about 30 wt. % solid silica, e.g., silica sold byDegussa under the trade names Aerosil or Ultrasil (a precipitated, spraydried silica containing about 90 wt. % silica), an aqueous colloidalsuspension of silica, for example one sold by Grace Davison under thetrade name Ludox, or HiSil (a precipitated hydrated SiO₂ containingabout 87 wt. % silica, about 6 wt. % free H₂O and about 4.5 wt. % boundH₂O of hydration and having a particle size of about 0.02 micro) favorscrystal formation from the above mixture. Preferably, therefore, theYO₂, e.g., silica, source contains about 30 wt. % solid YO₂, e.g.,silica, and more preferably about 40 wt. % solid YO₂, e.g., silica. Thesource of silicon may also be a silicate, e.g., an alkali metalsilicate, or a tetraalkyl orthosilicate.

In another embodiment, the synthesis mixture of this invention maycomprise at least one source of ions of trivalent element (X). Examplesof trivalent ion are aluminum, boron, iron, and/or gallium. The sourceof X, e.g., aluminum, is preferably aluminum sulphate or hydratedalumina. Other aluminum sources include, for example, otherwater-soluble aluminum salts, sodium aluminate, or an alkoxide, e.g.,aluminum isopropoxide, or aluminum metal, e.g., in the form of chips.

In one embodiment, the hydroxide source (OH⁻) is a material containinghydroxide ion (e.g., alkali metal hydroxide, ammonium hydroxide, andalkylamine hydroxide(s)), or a material generating hydroxide ion in thesynthesis mixture, such as alkali metal oxide. The alkali metal isadvantageously potassium or sodium, the sodium source advantageouslybeing sodium hydroxide or sodium aluminate.

Crystallization of the present crystalline material is carried out atstirred condition in a reactor vessel, such as for example, autoclaves.The speed of the stirring is measured by rotation per minute (RPM). Inone embodiment, the stirring speed is at least 1 RPM, preferably atleast 50 RPM, even more preferably, at least 100 RPM, and optionally atleast 500 RPM. The stirring rate required is a function of the tip speedof the stir blades which is determined by the geometry of the reactionvessel.

The total useful range of temperatures for crystallization is from about200° C. to about 500° C., preferably from about 210° C. to about 400°C., more preferably from about 250° C. to about 350° C. and mostpreferably from about 250° C. to about 300° C., for a time sufficientfor crystallization to occur at the temperature used, e.g. from about0.5 hour to about 72 hours, preferably from about 1 hour to about 48hours, more preferably from about 5 to 24 hours, and most preferablyfrom about 5 hours to about 12 hours. Thereafter, the crystals areseparated from the liquid and recovered.

It should be realized that the synthesis mixture components can besupplied by more than one source. The synthesis mixture can be preparedeither batchwise or continuously. Crystal size and crystallization timeof the new crystalline material will vary with the nature of thesynthesis mixture employed and the crystallization conditions.

Catalysis and Adsorption

A summary of the molecular sieves and/or zeolites, in terms ofproduction, modification and characterization of molecular sieves, isdescribed in the book “Molecular Sieves—Principles of Synthesis andIdentification”; (R. Szostak, Blackie Academic & Professional, London,1998, Second Edition). In addition to molecular sieves, amorphousmaterials, chiefly silica, aluminum silicate and aluminum oxide, havebeen used as adsorbents and catalyst supports. A number of long-knowntechniques, like spray drying, prilling, pelletizing and extrusion, havebeen and are being used to produce macrostructures in the form of, forexample, spherical particles, extrudates, pellets and tablets of bothmicropores and other types of porous materials for use in catalysis,adsorption and ion exchange. A summary of these techniques is describedin “Catalyst Manufacture,” A. B. Stiles and T. A. Koch, Marcel Dekker,New York, 1995.

To the extent desired, however, the original metal cations of theas-synthesized material can be replaced in accordance with techniqueswell known in the art, at least in part, by ion exchange with othercations. Preferred replacing cations include metal ions, hydrogen ions,hydrogen precursor, e.g., ammonium, ions and mixtures thereof.Particularly preferred cations are those which tailor the catalyticactivity for certain hydrocarbon conversion reactions. These includehydrogen, rare earth metals and metals of Groups IIA, IIIA, IVA, IB,IIB, IIIB, IVB and VIII of the Periodic Table of the Elements (IUPAC2001).

The crystalline material of this invention, when employed either as anadsorbent or as a catalyst in an organic compound conversion processshould be dehydrated, at least partially. This can be done by heating toa temperature in the range of 200° C. to 595° C. in an atmosphere suchas air, nitrogen, etc. and at atmospheric, subatmospheric orsuperatomspheric pressures for between 30 minutes and 48 hours.Dehydration can also be performed at room temperature merely by placingthe silicate in a vacuum, but a longer time is required to obtain asufficient amount of dehydration.

When used as a catalyst, the crystalline material of this inventionshould be subjected to thermal treatment to remove part of all of anyorganic constituent. The crystalline material can also be used as acatalyst in intimate combination with a hydrogenating component such astungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium,manganese, or a noble metal such as platinum or palladium where ahydrogenation-dehydrogenation function is to be performed. Suchcomponent can be in the composition by way of co-crystallization,exchanged into the composition to the extent a Group IIIA element, e.g.aluminum, is in the structure, impregnated therein or intimatelyphysically admixed therewith. Such component can be impregnated in or onto it such as, for example, by, in the case of platinum, treating thesilicate with a solution containing a platinum metal-containing ion.Thus, suitable platinum compounds for this purpose includechloroplatinic acid, platinous chloride and various compounds containingthe platinum amine complex.

The above crystalline material, especially in its metal, hydrogen andammonium forms can be beneficially converted to another form by thermaltreatment. This thermal treatment is generally performed by heating oneof these forms at a temperature of at least 370° C. for at least 1minute and generally not longer than 20 hours. While subatmosphericpressure can be employed for the thermal treatment, atmospheric pressureis desired for reasons of convenience. The thermal treatment can beperformed at a temperature up to about 925° C. The thermal treatedproduct is particularly useful in the catalysis of certain hydrocarbonconversion reactions. The thermally treated product, especially in itsmetal, hydrogen and ammonium forms, is particularly useful in thecatalysis of certain organic, e.g., hydrocarbon, conversion reactions.Non-limiting examples of such reactions include those described in U.S.Pat. Nos. 4,954,325; 4,973,784; 4,992,611; 4,956,514; 4,962,250;4,982,033; 4,962,257; 4,962,256; 4,992,606; 4,954,663; 4,992,615;4,983,276; 4,982,040; 4,962,239; 4,968,402; 5,000,839; 5,001,296;4,986,894; 5,001,295; 5,001,283; 5,012,033; 5,019,670; 5,019,665;5,019,664; and 5,013,422, each incorporated herein by reference as tothe description of said catalytic reactions.

The crystals of the crystalline material prepared by the instantinvention can be shaped into a wide variety of particle sizes. Generallyspeaking, the particles can be in the form of a powder, a granule, or amolded product, such as an extrudate. In cases where the catalyst ismolded, such as by extrusion, the crystals can be extruded before dryingor partially dried and then extruded.

The crystalline material of this invention may be used as an adsorbent,such as for separating at least one component from a mixture ofcomponents in the vapor or liquid phase having differential sorptioncharacteristics with respect to the crystalline material of thisinvention. Therefore, at least one component can be partially orsubstantially totally separated from a mixture of components havingdifferential sorption characteristics with respect to the crystallinematerial of this invention by contacting the mixture with thecrystalline material of this invention to selectively sorb the onecomponent.

The crystalline material of this invention can be used to catalyze awide variety of chemical conversion processes including many of presentcommercial/industrial importance. Specific examples of chemicalconversion processes which are effectively catalyzed by the crystallinematerial of this invention, by itself or in combination with one or moreother catalytically active substances including other crystallinecatalysts, include the following:

-   (a) alkylation of aromatic hydrocarbons, e.g., benzene, with long    chain olefins, e.g., C₁₄ olefin, with reaction conditions including    a temperature of from about 340° C. to about 500° C., a pressure of    from about 101 to about 20200 kPa-a, a weight hourly space velocity    of from about 2 hr⁻¹ to about 2000 hr⁻¹ and an aromatic    hydrocarbon/olefin molar ratio of from about 1/1 to about 20/1, to    provide long chain alkyl aromatics which can be subsequently    sulfonated to provide synthetic detergents;-   (b) alkylation of aromatic hydrocarbons with gaseous olefins to    provide short chain alkyl aromatic compounds, e.g., the alkylation    of benzene with propylene to provide cumene, with reaction    conditions including a temperature of from about 10° C. to about    125° C., a pressure of from about 101 to about 3030 kPa-a, and an    aromatic hydrocarbon weight hourly space velocity (WHSV) of from 5    hr⁻¹ to about 50 hr⁻¹;-   (c) alkylation of reformate containing substantial quantities of    benzene and toluene with fuel gas containing C₅ olefins to provide,    inter alia, mono- and dialkylates with reaction conditions including    a temperature of from about 315° C. to about 455° C., a pressure of    from about 3000 to about 6000 kPa-a, a WHSV-olefin of from about 0.4    hr⁻¹ to about 0.8 hr⁻¹, a WHSV-reformate of from about 1 hr⁻¹ to    about 2 hr⁻¹ and a gas recycle of from about 1.5 to 2.5 vol/vol fuel    gas feed;-   (d) alkylation of aromatic hydrocarbons, e.g. benzene, toluene,    xylene and naphthalene, with long chain olefins, e.g. C₁₄ olefin, to    provide alkylated aromatic lube base stocks with reaction conditions    including a temperature of from about 160° C. to about 260° C. and a    pressure of from about 2600 to 3500 kPa-a;-   (e) alkylation of phenols with olefins or equivalent alcohols to    provide long chain alkyl phenols with reaction conditions including    a temperature of from about 200° C. to about 250° C., a pressure of    from about 1500 to 2300 kPa-a and a total WHSV of from about 2 hr⁻¹    to about 10 hr⁻¹;-   (f) conversion of light paraffins to olefins and aromatics with    reaction conditions including a temperature of from about 425° C. to    about 760° C. and a pressure of from about 170 to about 15000 kPa-a;-   (g) conversion of light olefins to gasoline, distillate and lube    range hydrocarbons with reaction conditions including a temperature    of from about 175° C. to about 375° C. and a pressure of from about    800 to about 15000 kPa-a;-   (h) two-stage hydrocracking for upgrading hydrocarbon streams having    initial boiling points above about 260° C. to premium distillate and    gasoline boiling range products in a first stage using the    crystalline material of this invention in combination with a Group    VIII metal as catalyst with effluent therefrom being reaction in a    second stage using zeolite Beta, also in combination with a Group    VIII metal, as catalyst, the reaction conditions including a    temperature of from about 340° C. to about 455° C., a pressure of    from about 3000 to about 18000 kPa-a, a hydrogen circulation of from    about 176 to about 1760 liter/liter and a liquid hourly space    velocity (LHSV) of from about 0.1 to 10 hr⁻¹;-   (i) a combination hydrocracking/dewaxing process in the presence of    the crystalline material of this invention and a hydrogenation    component as catalyst, or a mixture of such catalyst and zeolite    Beta, with reaction conditions including a temperature of from about    350° C. to about 400° C., a pressure of from about 10000 to about    11000 kPa-a, an LHSV of from about 0.4 to about 0.6 and a hydrogen    circulation of from about 528 to about 880 liter/liter;-   (j) reaction of alcohols with olefins to provide mixed ethers, e.g.,    the reaction of methanol with isobutene and/or isopentene to provide    methyl-t-butyl ether (MTBE) and/or t-amyl methyl ether (TAM) with    conversion conditions including a temperature of from about 20° C.    to about 200° C. a pressure of from 200 to about 20000 kPa-a, a WHSV    (gram-olefin per hour gram-zeolite) of from about 0.1 hr⁻¹ to about    200 hr⁻¹ and an alcohol to olefin molar feed ratio of from about    0.1/1 to about 5/1;-   (k) toluene disproportionations with C₉+ aromatics as co-feed with    reaction conditions including a temperature of from about 315° C. to    about 595° C., a pressure of from about 101 to about 7200 kPa-a, a    hydrogen/hydrocarbon molar ratio of from about 0 (no added hydrogen)    to about 10 and a WHSV of from about 0.1 hr⁻¹ to about 30 hr;-   (l) preparation of the pharmaceutically-active compound    2-(4-isobutylphenyl) propionic acid, i.e. ibuprofen, by reacting    isobutylbenzene with propylene oxide to provide the intermediate    2-(4-isobutylphenyl)propanol followed by oxidation of the alcohol to    the corresponding carboxylic acid;-   (m) use as an acid-binding agent in the reaction of amines with    heterocyclic fiber-reactive components in preparation of dyes to    prepare practically salt-free reactive dye-containing solution, as    in German Patent No. DE 3,625,693, incorporated entirely herein by    reference;-   (n) as the absorbent for separating 2,6-toluene diisocyanate    (2,6-TDI) from isomers if TDI as in U.S. Pat. No. 4,721,807,    incorporated entirely herein by reference, whereby a feed mixture    comprising 2,6-TDI and 2,4-TDI is contacted with the present    crystalline material which has been cation-exchanged with K ions to    absorb the 2,6-TDI, followed by recovering the 2,6-TDI by desorption    with desorbent material comprising toluene;-   (o) as the absorbent for separating 2,4-TDI from its isomers as in    U.S. Pat. No. 4,721,806, incorporated entirely herein by reference,    whereby a feed mixture comprising 2,4-TDI and 2,6-TDI is contact    with the present crystalline material which has been    cation-exchanged with Na, Ca Li and/or Mg ions to absorb the    2,4-TDI, followed by recovering the 2,4-TDI by desorption with    desorbent material comprising toluene; and-   (p) in a process for decreasing the durene content of a 90-200° C.+    bottoms fraction obtained from the catalytic conversion of methanol    to gasoline which comprises contacting said durene-containing    bottoms fraction with hydrogen over a catalyst of the present    crystalline material with a hydrogenation metal, at conditions    including a temperature of from about 230° C. to about 425° C. and a    pressure of from about 457 to about 22000 kPa-a.

In an embodiment, the molecular sieves of this invention may be used inprocesses that co-produce phenol and ketones that proceed throughbenzene alkylation, followed by formation of the alkylbenzenehydroperoxide and cleavage of the alkylbenzene hydroperoxide into phenoland ketone. In such processes, the molecular sieves of this inventionare used in the first step, that is, benzene alkylation. Examples ofsuch processes includes processes in which benzene and propylene areconverted to phenol and acetone, benzene and C4 olefins are converted tophenol and methyl ethyl ketone, such as those described for example ininternational application PCT/EP2005/008557, benzene, propylene and C4olefins are converted to phenol, acetone and methyl ethyl ketone, which,in this case can be followed by conversion of phenol and acetone tobis-phenol-A as described in international applicationPCT/EP2005/008554, benzene is converted to phenol and cyclohexanone, orbenzene and ethylene are convened to phenol and methyl ethyl ketone, asdescribed for example in PCT/EP2005/008551.

The molecular sieves of this invention are useful in benzene alkylationreactions where selectivity to the monoalkylbenzene is required.Furthermore, the molecular sieves of this invention is particularlyuseful to produce selectively sec-butylbenzene from benzene and C4olefin feeds that are rich in linear butenes, as described ininternational application PCT/EP2005/008557. Preferably, this conversionis carried out by co-feeding benzene and the C4 olefin feed with thecatalyst of the present invention, at a temperature of about 60° C. toabout 260° C., for example of about 100° C. to 200° C., a pressure of7000 kPa-a or less, and a feed weight hourly space velocity (WHSV) basedon C4 alkylating agent of from about 0.1 to 50 hr⁻¹ and a molar ratio ofbenzene to C4 alkylating agent from about 1 to about 50.

The molecular sieves of this invention are also useful catalyst fortransalkylations, such as, for example, polyalkylbenzenetransalkylations.

In the case of many catalysts, it is desired to incorporate the newcrystal with another material resistant to the temperatures and otherconditions employed in organic conversion processes. Such materialsinclude active and inactive materials and synthetic or naturallyoccurring zeolites as well as inorganic materials such as clays, silicaand/or metal oxides such as alumina. The latter may be either naturallyoccurring or in the form of gelatinous precipitates or gels includingmixtures of silica and metal oxides. Use of a material in conjunctionwith the new crystal, i.e., combined therewith or present duringsynthesis of the new crystal, which is active, tends to change theconversion and/or selectivity of the catalyst in certain organicconversion processes. Inactive materials suitably serve as diluents tocontrol the amount of conversion in a given process so that products canbe obtained economically and orderly without employing other means forcontrolling the rate of reaction. These materials may be incorporatedinto naturally occurring clays, e.g., bentonite and kaolin, to improvethe crush strength of the catalyst under commercial operatingconditions. Said materials, i.e., clays, oxides, etc., function asbinders for the catalyst. It is desirable to provide a catalyst havinggood crush strength because in commercial use it is desirable to preventthe catalyst from breaking down into powder-like materials. These claybinders have been employed normally only for the purpose of improvingthe crush strength of the catalyst.

Naturally occurring clays which can be composited with the new crystalinclude the montmorillonite and kaolin family, which families includethe subbentonites, and the kaolins commonly known as Dixie, McNamee,Georgia and Florida clays or others in which the main mineralconstituent is halloysite, kaolinite, dictite, narcite, or anauxite.Such clays can be used in the raw state as originally mined or initiallysubjected to calcination, acid treatment or chemical modification.Binders useful for compositing with the present crystal also includeinorganic oxides, notably alumina.

In addition to the foregoing materials, the new crystal can becomposited with a porous matrix material such as silica-alumina,silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia,silica-titania as well as ternary compositions such assilica-alumina-thoria, silica-alumina-zirconia silica-alumina-magnesiaand silica-magnesia-zirconia.

The relative proportions of finely divided crystalline material andinorganic oxide matrix vary widely, with the crystal content in therange of from about 1 to about 90 percent by weight and more usually,particularly when the composite is prepared in the form of beads, in therange of about 2 to about 80 wt. % of the composite.

The following examples illustrate exemplary preferred embodiments:

EXAMPLES

The SEM images were obtained on a JEOL JSM-6340F Field Emission ScanningElectron Microscope (SEM), using a magnification at a voltage of 2 keV.

In these examples, the XRD diffraction patterns of the as-synthesizedmaterials were recorded on an X-Ray Powder Diffractometer using copperKα radiation in the 2θ range of 2 to 40 degrees.

Comparative Example A

A synthesis mixture was prepared containing the following ingredients: asodium aluminate solution (12.34 wt. % NaOH and 3.06 wt. % Al(OH)₃ inwater, Alcoa Corporation, Pittsburgh, Pa. USA), a 50 wt. % solution oftetraethyl ammonium bromide (R) in water (Sachem Chemicals), Ultrasil VN35P (92.4 wt. % of SiO₂ Degussa) and a 50 wt. % NaOH solution in water.The synthesis mixture had the following molar composition:

-   -   0.16Na₂O:0.033Al₂O₃:0.011R:SiO₂:58H₂O        The mixture was transferred to an autoclave and heated to        171° C. with a ramp rate of 25° C./hr, while stirring at 250        rotations per minute (“RPM”). The crystallization was continued        for 165 hrs at 171° C.

After crystallization a solid product was recovered from thecrystallization mixture, washed, and dried at 120° C. XRD analysis ofthe dried solid product showed it to be a mixture of mordenite andZSM-5. The yields, solids content, and hourly throughput are summarizedin Table 1 below.

Comparative Example B

A synthesis mixture was prepared containing the following ingredients: asodium aluminate solution (12.34 wt. % NaOH and 3.06 wt. % Al(OH)₃ inwater, Alcoa Corporation, Pittsburgh, Pa. USA), a 50 wt. % solution oftetraethyl ammonium bromide (R) in water (Sachem Chemicals), Ultrasil VN35P (92.4 wt. % of SiO₂, Degussa) and a 50 wt. % NaOH solution in water.The synthesis mixture had the following molar composition:

-   -   0.17Na₂O:0.036Al₂O₃:0.011R:SiO₂:25H₂O        The mixture was transferred to an autoclave and heated to        138° C. with a ramp rate of 25° C./hr, while stirring at 250        rotations per minute (“RPM”). The crystallization was continued        for 72 hrs at 138° C.

After crystallization a solid product was recovered from thecrystallization mixture, washed, and dried at 120° C. XRD analysis ofthe dried solid product showed it to be a mixture of mordenite andZSM-5. The yields, solids content, and hourly throughput are summarizedin Table 1 below.

Example 1

A synthesis mixture was prepared containing the following ingredients: asodium aluminate solution (12.34 wt. % NaOH and 3.06 wt. % Al(OH)₃ inwater, Alcoa Corporation, Pittsburgh, Pa., USA), a 60 wt. % solution oftriethylene tetraamine (R) in water (Sachem Chemicals), Ultrasil VN 35P(92.4 wt. % of SiO₂) and a 50 wt. % NaOH solution in water. Thesynthesis mixture had the following molar composition:

-   -   0.06Na₂O:0.05Al₂O₃:1.241R:SiO₂:20H₂O        The mixture was transferred to an autoclave and heated to        250° C. with a ramp rate of 25° C./hr. The crystallization was        continued for 8 hrs at 250° C.

After crystallization a solid product was recovered from thecrystallization mixture, washed, and dried at 120° C. XRD of the driedsolid product showed it to be a mixture of mordenite and ZSM-5. Theyields, solids content, and hourly throughput are summarized in Table 1below.

Comparative Example C

A synthesis mixture was prepared containing the following ingredients: asodium tetraborate decahydrate (NaB₄O₇.10H₂O), a 50 wt. % solution oftetraethyl ammonium bromide (R) in water (Sachem Chemicals). Ultrasil VN35P (92.4 wt. % of SiO₂) and a 50 wt. % NaOH solution in water. Thesynthesis mixture had the following molar composition:

-   -   0.0315Na₂O:0.0013B₂O₃:0.01R:SiO₂:21H₂O        The mixture was transferred to an autoclave and heated to        160° C. with a ramp rate of 25° C./hr. The crystallization was        continued for 72 hrs at 160° C.

After crystallization a solid product was recovered from thecrystallization mixture, washed, and dried at 120° C. XRD of the driedsolid product showed it to be ZSM-50. The yields, solids content, andhourly throughput are summarized in Table 1 below.

Example 2

A synthesis mixture was prepared containing the following ingredients: asodium tetraborate decahydrate (NaB₄O₇.10H₂O), a 50 wt. % solution oftetraethyl ammonium bromide (R) in water (Sachem Chemicals). Ultrasil VN35P (92.4 wt. % of SiO₂) and a 50 wt. % NaOH solution in water. Thesynthesis mixture had the following molar composition:

-   -   0.085Na₂O:0.0013B₂O₃:0.01R:SiO₂:6.88H₂O        The mixture was transferred to an autoclave and heated to        240° C. with a ramp rate of 25° C./hr. The crystallization was        continued for 24 hrs at 240° C.

After crystallization a solid product was recovered from thecrystallization mixture, washed, and dried at 120° C. XRD (FIG. 1) ofthe dried solid product showed it to be ZSM-50. The SEM image (FIG. 2)of the solid product showed cubic morphology. The yields, solidscontent, and hourly throughput are summarized in Table 1 below.

Comparative Example D

A synthesis mixture was prepared containing the following ingredients: asodium aluminate solution (12.34 wt. % NaOH and 3.06 wt. % Al(OH)₃ inwater, Alcoa Corporation, Pittsburgh, Pa., USA), a 50 wt. % solution oftetraethyl ammonium bromide (R) in water (Sachem Chemicals), Ultrasil VN35P (92.4 wt. % of SiO₂) and a 50 wt. % NaOH solution in water. Thesynthesis mixture had the following molar composition:

-   -   0.075Na₂O:0.0035Al₂O₃:0.34R:SiO₂:18H₂O        The mixture was transferred to an autoclave and heated to        138° C. with a ramp rate of 25° C./hr. The crystallization was        continued for 72 hrs at 138° C.

After crystallization a solid product was recovered from thecrystallization mixture, washed, and dried at 120° C. XRD of the driedsolid product showed it to be ZSM-5. The yields, solids content andhourly throughput are summarized in Table 1 below.

Example 3

A synthesis mixture was prepared containing the following ingredients: asodium aluminate solution (12.34 wt. % NaOH and 3.06 wt. % Al(OH)₃ inwater. Alcoa Corporation, Pittsburgh, Pa., USA), a 50 wt. % solution oftetraethyl ammonium bromide (R) in water (Sachem Chemicals). Ultrasil VN35P (92.4 wt. % of SiO₂) and a 50 wt. % NaOH solution in water. Thesynthesis mixture had the following molar composition:

-   -   0.055Na₂O:0.0036Al₂O₃:0.19R:SiO₂:13.6H₂O        The mixture was transferred to an autoclave and heated to        240° C. with a ramp rate of 25° C./hr. The crystallization was        continued for 24 hrs at 240° C.

After crystallization a solid product was recovered from thecrystallization mixture, washed, and dried at 120° C. XRD of the driedsolid product showed it to be ZSM-5. The yields, solids content, andhourly throughput are summarized in Table 1 below.

Comparative Example E

A synthesis mixture was prepared from water, Hexamethyleneimine (HMI)solution, Ultrasil Modified, sodium aluminate solution, and 50 wt. %sodium hydroxide solution The synthesis mixture had the following molarcomposition:

-   -   0.085Na₂O:0.0033Al₂O₃:0.35R:SiO₂:20H₂O

The mixture was crystallized at 150° C. in an autoclave with stirring at250 RPM for 72 hours. After crystallization, the synthesis mixtureslurry was filtered, washed with deionized (DI) water and dried at 120°C. The XRD patterns of the as-synthesized material showed the typicalpure phase of MCM-22 topology. The resulting MCM-22 crystals had aSiO₂/Al₂O₃ molar ratio of ˜23/1. The yields, solids content, and hourlythroughput are summarized in Table 1 below.

Example 4

A synthesis mixture was prepared from water, Hexamethyleneimine (HMI)solution. Ultrasil, sodium aluminate solution, and 50 wt. % sodiumhydroxide solution. The mixture had the following molar composition:

-   -   0.075Na₂O:0.0032Al₂O₃:0.2R:SiO₂:12.70H₂O

The mixture was crystallized at 205° C. in an autoclave with stirring at250 RPM for 20 hours. After crystallization, the synthesis mixtureslurry was filtered, washed with deionized (DI) water and dried at 120°C. The XRD patterns of the as-synthesized material showed MCM-22topology with ZSM-5 impurity. ZSM-5 impurity was estimated to be <10% inthe resulting product. The resulting MCM-22 crystals had a SiO₁/Al₂O₃molar ratio of ˜24. The yields, solids content, and hourly throughputare summarized in Table 1 below.

TABLE 1 Weight Weight hourly hourly Solid- throughput template contentTime based on SiO₂ Temperature efficiency Example (wt. %) (hrs) (hr⁻¹)*(° C.) (hr⁻¹)* A 5.7% 165 0.00030 171 0.014 B 13.3% 72 0.00157 138 0.0131 16.7% 8 0.01771 250 0.038 C 15.9% 72 0.00187 160 0.03 2 48.4% 240.01716 240 0.089 D 18.5% 72 0.00219 138 0.01 3 24.5% 24 0.00868 2400.054 E 16.7% 72 0.00197 150 0.022 4 26.2% 20 0.01115 205 0.136*Estimate at 85% SiO₂ utilization

All patents, patent applications, test procedures, priority documents,articles, publications, manuals, and other documents cited herein arefully incorporated by reference to the extent such disclosure is notinconsistent with the present invention and for all jurisdictions inwhich such incorporation is permitted.

When numerical lower limits and numerical upper limits are listedherein, ranges from any lower limit to any upper limit are contemplated.

While the illustrative embodiments of this invention have been describedwith particularity, it will be understood that various othermodifications will be apparent to and can be readily made by thoseskilled in the art without departing from the spirit and scope of thisinvention. Accordingly, it is not intended that the scope of the claimsappended hereto be limited to the examples and descriptions set forthherein but rather that the claims be construed as encompassing all thefeatures of patentable novelty which reside in the present invention,including all features which would be treated as equivalents thereof bythose skilled in the art to which this invention pertains.

1-54. (canceled)
 55. A process for converting hydrocarbons comprisingthe step of contacting said hydrocarbons under conversion conditionswith a crystalline molecular sieve, said crystalline molecular sievecomposition having a pore size in the range of from about 2 to about 19Å and made by a method comprising the steps of: (a) providing a mixturecomprising at least one source of ions of tetravalent element (Y), atleast one hydroxide source (OH⁻), at least one structure—directing agent(template), and water, said mixture having a solid-content in the rangeof from about 15% to about 50%, wherein said solid-content is measuredas the weight of said tetravalent element and said weight of saidtrivalent element express in terms of their oxides divided by the weightof said water in said mixture as a percentage as follows:${{{solid}\text{-}{content}} = \frac{\begin{matrix}{{said}\mspace{14mu} {weight}\mspace{14mu} {of}\mspace{14mu} {said}\mspace{14mu} {oxides}} \\{{in}\mspace{14mu} {said}\mspace{14mu} {mixture} \times 100\%}\end{matrix}}{{said}\mspace{14mu} {weight}\mspace{14mu} {of}\mspace{14mu} {said}\mspace{14mu} {oxides}\mspace{14mu} {in}\mspace{14mu} {said}\mspace{14mu} {mixture}}};$and (b) treating said mixture with stirring at crystallizationconditions sufficient to obtain a weight hourly throughput from about0.005 to about 1 hr⁻¹, and a weight hourly template efficiency of atleast about 0.05 hr⁻¹ to form said crystalline molecular sieve, whereinsaid crystallization conditions comprise a temperature in the range offrom about 200° C. to about 500° C. and a crystallization time less than100 hr, wherein said crystalline molecular sieve has a zeolite frameworktype comprising at least one of ABW, AEI, AEL, AET, AFI, AFO, CHA, EMT,FAU, FER, LEV, LTA, LTL, MAZ, MEL, MTT, NES, OFF, TON, VFI, MWW, MTW,MOR, EUO, *BEA, and MFS, wherein said weight hourly template efficiencyis calculated by dividing the weight of the molecular sieve produced inthe dried cake with the weight of the directing agent used in thesynthesis mixture and the total time required for the crystallization asfollows: ${\begin{matrix}{{weight}\mspace{14mu} {hourly}} \\{{template}\mspace{14mu} {efficiency}}\end{matrix} = \frac{\begin{matrix}{{weight}\mspace{14mu} {of}\mspace{14mu} {the}\mspace{14mu} {oxide}\mspace{14mu} {of}} \\{{tetravalent}\mspace{14mu} {element}\mspace{14mu} \left( {YO}_{2} \right) \times} \\{{tetravalent}\mspace{14mu} {element}\mspace{14mu} {oxide}\mspace{14mu} {utilization}}\end{matrix}}{\begin{matrix}{\left( {{weight}\mspace{14mu} {of}\mspace{14mu} {the}\mspace{14mu} {directing}\mspace{14mu} {agent}} \right) \times} \\\left( {{crystallization}\mspace{14mu} {time}} \right)\end{matrix}}},$ and said tetravalent element oxide utilization is 0.85.56. The process recited in claim 55, wherein said weight hourlythroughput is in the range of from about 0.008 to about 1 hr⁻¹.
 57. Theprocess recited in claim 55, wherein said temperature range is fromabout 225° C. to about 250° C.
 58. The process recited in claim 55,wherein said mixture further comprises from about 0.01 to 20 wt. % basedon the total weight of said mixture of at least one seed source (Seed).59. The process recited in claim 55, wherein said mixture furthercomprises from about 0.01 to 10 wt. % based on the total weight of saidmixture of at least one seed source (Seed).
 60. The process recited inclaim 55, wherein said mixture further comprises at least one source ofions of trivalent element.
 61. The process recited in claim 60, whereinsaid trivalent element is aluminum.
 62. The process recited in claim 61,wherein said crystallization temperature is in the range of from about200° C. to about 300° C., and crystallization time is less than 72 hr.63. The process recited in claim 1, wherein said crystallizationtemperature is in the range of from about 200° C. to about 250° C., andcrystallization time is less than 48 hr.
 64. The process recited inclaim 55, wherein said crystallization temperature is in the range offrom about 200° C. to about 250° C., and crystallization time is lessthan 10 hr.
 65. The process recited in claim 55, wherein saidcrystallization temperature is in the range of from about 200° C. toabout 250° C., and crystallization time is less than 5 hr.
 66. Theprocess recited in claim 55, wherein said crystalline molecular sievecomprises at least one of mordenite, MCM-22, MCM-49, MCM-56, ZSM-57,ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-30, ZSM-50, ZSM-48, ETS-10, ETAS-10,and ETGS-10.
 67. The process recited in claim 55, wherein saidtetravalent element is silicon.
 68. The process recited in claim 55,further comprising: (c) separating said crystalline molecular sieve fromsaid mixture.
 69. The process recited in claim 55, wherein saidcrystalline molecular sieve formed in step (b) is substantially free ofnon-crystalline material.
 70. The process recited in claim 55, whereinsaid solid-content range is from about 20% to about 30%.
 71. The processrecited in claim 55, wherein said solid-content range is from about 24%to about 26%.